The invention relates to novel crosslinkable, photoactive polymers from the class of polyimides, polyamide acids and esters thereof, and to their use as orientation layers for liquid crystals and in the construction of unstructured and structured optical elements and multi-layer systems.
In (electro-optical) liquid crystal devices the orientation layer is of particular importance. It serves to ensure a uniform and trouble-free alignment of the longitudinal axes of the molecules.
For the orientation of liquid crystal molecules in liquid crystal displays (LCDs) it is customary to use uniaxially rubbed polymer orientation layers, such as, for example, polyimide. The direction of rubbing in that process gives the direction of orientation. Especially for use in LCDs, however, in addition to giving the direction of orientation it is also necessary for an angle of tilt to be imparted by the orientation layer. That angle can be produced on the mentioned polymer surfaces likewise by the rubbing process. When a liquid crystal is brought into contact with such a surface, the liquid crystal molecules do not lie parallel to the surface but at an angle thereto, that is to say the angle of tilt is transferred to the liquid crystal. The size of the angle of tilt is determined both by rubbing parameters, such as, for example, rate of advance and contact pressure, and by the chemical structure of the polymer. For the production of liquid crystal displays, angles of tilt of between 1xc2x0 and 15xc2x0 are required, depending upon the type of display. The larger angles of tilt are required especially for supertwisted nematic (STN) LCDs in order to avoid the formation of so-called fingerprint textures. In TN and TFT-TN LCDs, the direction of rotation and of tilting is defined by the angle of tilt, so that xe2x80x9creverse twistxe2x80x9d and xe2x80x9creverse tiltxe2x80x9d phenomena are prevented. Whereas, in the switched-off state, reverse twist results in areas having the incorrect direction of rotation (which manifests itself optically in the display having a spotty appearance), reverse tilt becomes particularly apparent when the LCD is switched on, causing very troublesome optical effects as a result of the liquid crystals tilting in different directions. Reverse twist can be prevented by doping the liquid crystal mixture with a chiral doping agent. To suppress reverse tilt there has hitherto been no alternative to the use of orientation layers having an angle of tilt.
The above-described orientation by rubbing is associated with some serious disadvantages, however, that can have a marked effect on the optical quality of the liquid crystal displays. For example, the rubbing process produces dust which can result in optical defects in the display. At the same time the polymer layer becomes electro-statically charged, which may, for example in the case of thin film transistor.(TFT)-TN LCDs, result in the destruction of the underlying thin layer transistors. For those reasons the yield of displays that are free of optical defects has not been optimum in LCD production hitherto.
A further disadvantage of the rubbing process is that it is not possible to produce structured orientation layers in a simple manner, since local variation of the direction of orientation is not possible in the rubbing process. Rubbing is therefore used chiefly to produce layers having uniform alignment over a large area. Structured orientation layers are of great interest, however, in many areas of display technology and integrated optics. For example, they can be used in improving the viewing angle dependency of twisted nematic (TN) LCDs.
To improve viewing angle dependency,. LCDs having pixels that alternate in respect of angle of tilt were proposed some time ago (e.g. EP-A-0 683 418). That proposal was based on the realisation that the angles of tilt of polyimide layers change at sites which have been irradiated beforehand with laser light. That change is based on the destruction of some of the imide bonds at the site of irradiation, for which purpose comparatively short wavelengths and high light intensities are required. Using that procedure it is possible in principle to produce orientation layers having domains with different angles of tilt. The disadvantages lie, however, in the high irradiation energy required for the purpose and the comparatively long irradiation time. In addition, the orientation of the longitudinal axes of the molecules in the plane of the layer is produced, as before, by rubbing, so that the above-mentioned problems arising in the rubbing process cannot be eliminated. In particular, that procedure cannot be used to produce structured surface orientations.
Orientation layers in which the direction of orientation can be predetermined by irradiation with polarised light have been known for some time. It is by that means possible to avoid the problems inherent in the rubbing process. In addition, it is possible to provide areas having different directions of orientation and thus to structure the orientation layer.
One possible method for the structured orientation of liquid crystals utilises the isomerisation capacity of certain dye molecules to induce a preferred direction photo-chemically by irradiation with polarised light of a suitable wavelength. This is achieved, for example, by mixing a dye into an orientation polymer, which is then irradiated with polarised light. Such a guest/host system is described, for example, in U.S. Pat. No. 4,974,941. In that system, azobenzenes are mixed into polyimide orientation layers and then irradiated with polarised light. Liquid crystals that are in contact with the surface of a layer so irradiated become oriented in accordance with that preferred direction. That orientation process is reversible, that is to say by further irradiation of the layer with light of a second direction of polarisation it is possible for the direction of orientation that has already been established to be changed round again. Since that reorientation process can be repeated as often as desired, orientation layers on that basis are less suitable for use in LCDs.
Another possible method of producing high-resolution orientation patterns in liquid crystalline layers is described in Jpn. J. Appl. Phys., Vol. 31 (1992), 2155. In that process the dimerisation of polymer-bonded photoreactive cinnamic acid groups induced by irradiation with linearly polarised light is employed for the structured orientation of liquid crystals. Unlike the reversible orientation procedure described above, in the case of the photostructurable orientation layers described in Jpn. J. Appl. Phys., Vol. 31 (1992), 2155 an anisotropic polymer network is synthesised. Those photo-oriented polymer networks can be used wherever structured or unstructured liquid crystal orientation layers are required. In addition to their use in LCDs, such orientation layers can also be used, for example, in the production of so-called hybrid layers, as exemplified in European Patent Applications EP-A-0 611 981, EP-A-0 689 084, EP-A-0 689 065 and EP-A-0 753 785. Using those hybrid layers of photostructured orientation polymers and crosslinkable low molecular weight liquid crystals it is possible to realise optical elements such as, for example, non-absorptive colour filters, linear and circular polarisers, optical delay layers and so on.
EP-A-0 611 786, EP-A-0 763 552 and WO-A-96/10049 describe cinnamic acid polymers that are suitable in, principle for the synthesis of such anisotropically crosslinked, photostructured orientation layers for liquid crystals. In the case of the compounds described in EP-A-0 763 552 and WO-A-96/10049, on irradiation with linearly polarised light it is possible, in addition to inducing the desired orientation, simultaneously to induce an angle of tilt. It is thus possible to produce layers having structuring in respect of surface orientation and angle of tilt.
The orientation layers formed from the polymers described in EP-A-0 611 786, EP-A-0 763 552 and WO-A-96/10049 have the disadvantage, however, that for certain applications, especially for use in TFT displays, they result in the adjacent liquid crystal mixture having an insufficient electrical resistance value. In TFT displays, too low a resistance value of the liquid crystal medium leads to an inadequate xe2x80x9cholding ratioxe2x80x9d, which is a measure of the voltage drop in the display after the voltage has been switched off. Low holding ratio values, however, bring about undesirable changes in brightness and contrast over time and thus result in unstable graduations of the grey tones.
The problem underlying the invention was, therefore, to produce photoreactive polymers that, when irradiated with polarised light, result in the production of stable, high-resolution orientation patterns having a defined angle of tilt and at the same time result in sufficiently high resistance values (holding ratios) in the adjacent liquid crystal medium.
Surprisingly, it has now been found that polyimides that have in addition as side-chains groups derivable structurally from 3-arylacrylic acid are able to fulfil those conditions and are excellently suitable as orientation layers for liquid crystals. The crosslinking of those compounds using linearly polarised light results in excellent orientation of the liquid crystals, in an angle of tilt that can be set by the irradiation conditions and, at the same time, in an appreciable increase in the electrical resistance and holding ratio in the neighbouring liquid crystal medium.
The present invention therefore relates to side-chain polymers from the class of polyimides, polyamide acids and esters thereof, characterised in that they comprise as side-chains photocrosslinkable groups of the general formula I: 
wherein the broken line indicates the point of linkage to the polymer main chain and wherein:
A, B each independently of the other represents unsubstituted or optionally fluoro-, chloro-, cyano-, alkyl-, alkoxy-, fluoroalkyl- or fluoroalkoxy-substituted phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, cyclohexane-1,4-diyl, piperidine-1,4-diyl, piperazine-1,4-diyl;
C represents unsubstituted or optionally fluoro-, chloro-, cyano-, alkyl-, alkoxy-, fluoroalkyl- or fluoroalkoxy-substituted phenylene, or pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene;
D represents xe2x80x94OR1xe2x80x94, xe2x80x94NR1xe2x80x94, or an oxygen atom linked to ring C in the ortho-position to form a coumarin unit, wherein R1 is an optionally fluoro- or chloro-substituted straight-chain or branched alkyl group having from 1 to 20 carbon atoms or an optionally fluoro-, chloro-, alkyl- or alkoxy-substituted cycloalkyl radical having from 3 to 8 ring atoms;
S1 represents a single covalent bond or a spacer unit, such as a straight-chain or branched alkylene grouping represented by xe2x80x94(CH2)rxe2x80x94, optionally mono- or poly-substituted by fluorine, chlorine or cyano, or a chain of the formula Lxe2x80x94(CH2)rxe2x80x94L2xe2x80x94 or L1xe2x80x94(CH2)rxe2x80x94L2xe2x80x94(CH2)sxe2x80x94L3xe2x80x94, wherein L1, L2 and L3 each independently of the others represents a single bond or linking functional groups such as xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, wherein R2 represents hydrogen or lower alkyl and r and s are each an integer from 1 to 20, with the proviso that r+sxe2x89xa624;
S2 represents a single covalent bond or a spacer unit, such as a straight-chain or branched alkylene grouping represented by xe2x80x94(CH2)rxe2x80x94, optionally mono- or poly-substituted by fluorine, chlorine or cyano, or a chain of the formula xe2x80x94(CH2)rxe2x80x94L1 xe2x80x94 or xe2x80x94(CH2)rxe2x80x94L1xe2x80x94(CH2)sxe2x80x94L2xe2x80x94, wherein L1 and L2 each independently of the other represents a single bond or linking functional groups such as xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, wherein R2 represents hydrogen or lower alkyl and r and s are each an integer from 1 to 20, with the proviso that r+sxe2x89xa624;
X, Y each independently of the other represents hydrogen, fluorine, chlorine, cyano, optionally fluoro-substituted alkyl having from 1 to 12 carbon atoms in which optionally one CH2 group or two or more non-adjacent CH2 groups may have been replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94 and/or xe2x80x94CHxe2x95x90CHxe2x80x94;
Z1, Z2 each independently of the other represents a single covalent bond, xe2x80x94(CH2)txe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94NR3xe2x80x94, xe2x80x94COxe2x80x94NR3xe2x80x94, xe2x80x94R3Nxe2x80x94COxe2x80x94, xe2x80x94(CH2)uxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)uxe2x80x94, xe2x80x94(CH2)uxe2x80x94NR3xe2x80x94 or xe2x80x94NR3xe2x80x94(CH2)uxe2x80x94; R3 representing hydrogen or lower alkyl;
t represents an integer from 1 to 4;
u represents an integer from 1 to 3;
m represents 0 or 1;
n represents 0 or 1.
The term xe2x80x9cpolyimidexe2x80x9d will be familiar to the person skilled in the art and is frequently used in the polymer literature, see, for example: Polyimides, Ed. K. L. Mittal, Vol. 1 and 2, 1984. It denotes a polymer the chain of which has been synthesised from a number of identical or different building blocks (monomers) in such a manner that the building blocks are linked to one another by imide bonds. Since the polyimides are generally synthesised by an imidisation reaction, for example by thermal condensation, from the corresponding polyamide, acids or from esters of the corresponding polyamide acids, such polyimides may contain, in addition to the imide groups, also proportions of amide acid groups or amide acid ester groups as linking functionalities. In addition, polyamide acids and polyamide acid esters that contain side-chains of the general formula I are important novel precursors of the polyimides according to the invention. They are therefore likewise a subject of the present invention.
The term xe2x80x9clower alkylxe2x80x9d, taken on its own or in a combination such as xe2x80x9clower alkoxyxe2x80x9d, denotes straight-chain and branched saturated hydrocarbon radicals having from 1 to 6, preferably from 1 to 3, carbon atoms, such as methyl, ethyl, propyl or isopropyl and the like.
The term xe2x80x9calkylxe2x80x9d, taken on its own or in a combination such as xe2x80x9calkoxyxe2x80x9d, denotes straight-chain and branched saturated hydrocarbon radicals having up to 20 carbon atoms.
The term xe2x80x9cfluoroalkylxe2x80x9d denotes an alkyl radical as defined above wherein the hydrocarbon radicals are mono- or poly-substituted by fluorine. Examples of fluoroalkyl groups are: 2-fluoroethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 1H, 1H-pentadecafluorooctyl, 1H,1H,7H-dodecafluoroheptyl, 2-(perfluorooctyl)ethyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorodecyl)ethyl, perfluoropropyl, perfluorobutyl, perfluoroheptyl, perfluorooctyl, perfluorononyl.
The term xe2x80x9cfluoroalkoxyxe2x80x9d denotes an alkoxy radical as defined above wherein the hydrocarbon radicals are mono- or poly-substituted by fluorine. Examples of fluoroalkoxy groups are: 1-fluoropropoxy, 1-fluoropentyloxy, 2-fluoropropoxy, 2,2-difluoropropoxy, 3-fluoropropoxy, 3,3-difluoropropoxy, 3,3,3-trifluoropropoxy, trifluoromethoxy.
Preferred xe2x80x9cspacer unitsxe2x80x9d S1 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2) sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)s xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa620, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S1 are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 3-propyleneoxy, 3-propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentyleneoxy, 5-pentyleneoxycarbonyl, 4-butylenecarbonyloxy, 6-hexyleneoxy, 6-hexyleneoxycarbonyl, 5-pentylenecarbonyloxy, 7-heptyleneoxy, 7-heptyleneoxycarbonyl, 6-hexylenecarbonyloxy, 8-octyleneoxy, 8-octyleneoxycarbonyl, 7-heptylenecarbonyloxy, 9-nonyleneoxy, 9-nonyleneoxycarbonyl, 8-octylenecarbonyloxy, 10-decyleneoxy, 10-decyleneoxycarbonyl, 9-nonylenecarbonyloxy, 11-undecyleneoxy, 11-undecyleneoxycarbonyl, 10-decylenecarbonyloxy, 12-dodecyleneoxy, 12-dodecyleneoxycarbonyl, 11-undecylenecarbonyloxy, 3-propyleneiminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleneiminocarbonyl, 6-hexyleneiminocarbonyl, 7-heptyleneirninocarbonyl, 8-octyleneiminocarbonyl, 9-nonyleneiminocarbonyl, 1 0-decyleneiminocarbonyl, 11-undecyleneiminocarbonyl, .12-dodecyleneiminocarbonyl, 2-ethylenecarbonylimino, 3-propylenecarbonylimino, 4-butylenecarbonylimino, 5-pentylenecarbonylimino, 6-hexylenecarbonylimino, 7-heptylenecarbonylimino, 8-octylenecarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneoxy)hexylene, 6-(3-propyleneoxy)hexyleneoxy, 6-(3-propyleneiminocarbonyloxy)hexyleneoxy, 6-(3-propyleneiminocarbonyl)hexylene, 6-(3-propyleneiminocarbonyl)hexyleneoxy, 1,2-ethylenedioxy, 1,3-propylenedioxy, 1,4-butylenedioxy, 1,5-pentylenedioxy, 1,6-hexylenedioxy, 1,7-heptylenedioxy, 1,8-octylenedioxy, 1,9-nonylenedioxy, 1,10-decylenedioxy, 1,11-undecylenedioxy, 1,12-dodecylenedioxy and the like.
Especially preferred xe2x80x9cspacer unitsxe2x80x9d S1 are a straight-chain alkylene grouping represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94NHxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94NHxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94O xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, wherein r and s are each an integer from 2 to 12 and the sum of r+sxe2x89xa615.
Preferred xe2x80x9cspacer unitsxe2x80x9d S2 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94O xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2) sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa620, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S2 are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 3-propyleneoxy, 3-propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentyleneoxy, 5-pentyleneoxycarbonyl, 4-butylenecarbonyloxy, 6-hexyleneoxy, 6-hexyleneoxycarbonyl, 5-pentylenecarbonyloxy, 7-heptyleneoxy, 7-heptyleneoxycarbonyl, 6-hexylenecarbonyloxy, 8-octyleneoxy, 8-octyleneoxycarbonyl, 7-heptylenecarbonyloxy, 9-nonyleneoxy, 9-nonyleneoxycarbonyl, 8-octylenecarbonyloxy, 10-decyleneoxy, 10-decyleneoxycarbonyl, 9-nonylenecarbonyloxy, 11-undecyleneoxy, 11-undecyleneoxycarbonyl, 10-decylenecarbonyloxy, 12-dodecyleneoxy, 12-dodecyleneoxycarbonyl, 11-undecylenecarbonyloxy, 3-propyleneiminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleneiminocarbonyl, 6-hexyleneiminocarbonyl, 7-heptyleneiminocarbonyl, 8-octyleneiminocarbonyl, 9-nonyleneiminocarbonyl, 10-decyleneiminocarbonyl, 11-undecyleneiminocarbonyl, 12-dodecyleneiminocarbonyl, 2-ethylenecarbonylimino, 3-propylenecarbonylimino, 4-butylenecarbonylimino, 5-pentylenecarbonylimino, 6-hexylenecarbonylimino, 7-heptylenecarbonylimino, 8-octylenecarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneoxy)hexylene, 6-(3-propyleneoxy)hexyleneoxy, 6-(3-propyleneiminocarbonyloxy)hexyleneoxy, 6-(3-propyleneiminocarbonyl)hexylene, 6-(3-propyleneiminocarbonyl)hexyleneoxy and the like.
Especially preferred xe2x80x9cspacer unitsxe2x80x9d S2 are a straight-chain alkylene grouping represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94, wherein r and s are each an integer from 2 to 12 and the sum of r+sxe2x89xa615.
The expression xe2x80x9cunsubstituted or optionally fluoro-, chloro-, cyano-, alkyl- or alkoxy-substituted phenylenexe2x80x9d includes in the context of the present invention 1,2-, 1,3-or 1,4-phenylene that is unsubstituted or mono- or poly-substituted by fluorine, chlorine, cyano, alkyl or alkoxy, preferably by fluorine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy or cyano. Preference is given to 1,3- or 1,4-phenylene, but especially to 1,4-phenylene.
Examples of preferred phenylene radicals are 1,3- or 1,4-phenylene, 4- or 5-methyl-1,3-phenylene, 4- or 5-methoxy-1,3-phenylene, 4- or 5-ethyl-1,3-phenylene, 4- or 5-ethoxy-1,3-phenylene, 2- or 3-methyl-1,4-phenylene, 2- or 3-ethyl-1,4-phenylene, 2- or 3-propyl-1,4-phenylene, 2- or 3-butyl-1,4-phenylene, 2- or 3-methoxy-1,4-phenylene, 2- or 3-ethoxy-1,4-phenylene, 2- or 3-propoxy-1,4-phenylene, 2- or 3-butoxy-1,4-phenylene, 2,3-, 2,6- or 3,5-dimethyl-1,4-phenylene, 2,6- or 3,5-dimethoxy-1,4-phenylene, 2- or 3-fluoro-1,4-phenylene, 2,3-, 2,6- or 3,5-difluoro-1,4-phenylene, 2- or 3-chloro-1,4-phenylene, 2,3-, 2,6- or 3,5-dichloro-1,4-phenylene, 2- or 3-cyano-1,4-phenylene and the like.
The preferred side-chains of the formula I can be further divided into:
a) side-chains of the forrnula I having three rings A, B and C;
b) side-chains of the formula I having two rings A and C or B and C;
c) side-chains of the formula I having the ring C.
Of those, the groups listed under b) and c) are especially preferred.
Also preferred are those side-chains of the formula I wherein X and Y represent hydrogen.
Preference is accordingly given to the side-chains of the formula II: 
wherein A, B, C, D, S1, S2, Z1, Z2, m and n have the meanings given under formula I.
Special preference is given to the side-chains of formula II wherein S1, S2, m and n have the meanings given under formula I and wherein:
Z1, Z2 represent a single covalent bond, xe2x80x94CH2CH2xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94, xe2x80x94COxe2x80x94COxe2x80x94Oxe2x80x94 or xe2x80x94Oxe2x80x94COxe2x80x94;
A, B each independently of the other represents unsubstituted or optionally alkyl-, fluoroalkyl-, alkoxy- or fluoroalkoxy-substituted phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl or cyclohexane-1,4-diyl;
C represents unsubstituted or optionally fluoro-, alkyl-, fluoroalkyl-, alkoxy- or fluoroalkoxy-substituted phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5-furanylene, or 1,4- or 1,6-naphthylene;
D represents xe2x80x94OR1xe2x80x94, xe2x80x94NR1xe2x80x94, or an oxygen atom linked to ring C in the ortho-position to form a coumarin unit, wherein R1 is a straight-chain or branched alkyl group having from 1 to 12 carbon atoms or an optionally alkyl- or alkoxy-substituted cycloalkyl radical having 5 or 6 ring atoms.
Preferred monomer units from which the main chains of the side-chain polymers according to the invention are generally synthesised are the imide groups of the general formulae III, V and VII and/or the analogous amide acid groups and amide acid ester groups of the general formulae IV, VI and VIII: 
in which the broken line symbolises, as appropriate, the linkage to one or two crosslinkable side-chains of the general formula I;
T1 represents the tetravalent organic radical of a tetracarboxylic acid dianhydride after formal removal of the two xe2x80x94COxe2x80x94Oxe2x80x94COxe2x80x94 groups, the four valencies of which are distributed between four different carbon atoms of the radical;
T2, T3 each independently of the other represents an unsubstituted or optionally fluoro-, chloro-, cyano-, alkyl-, alkoxy-, fluoroalkyl- or fluoroalkoxy-substituted aromatic, aliphatic or alicyclic trivalent group, the three valencies of which are distributed between three different carbon atoms of the group;
S3 represents a single covalent bond or a divalent group, such as straight-chain or branched alkylene groupings represented by xe2x80x94(CH2)rxe2x80x94, optionally mono- or poly-substituted by fluorine, chlorine or cyano, or a chain of the formula xe2x80x94(CH2)rxe2x80x94L1xe2x80x94 or xe2x80x94(CH2)rxe2x80x94L1xe2x80x94(CH2)sxe2x80x94L2xe2x80x94, wherein L1 and L2 represent a single bond or linking functional groups such as xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, R2 represents hydrogen or lower alkyl and r and s are each an integer from 1 to 20, with the proviso that r+sxe2x89xa624;
S4, S7 each independently of the other represents a single covalent bond or divalent groups, such as straight-chain or branched alkylene groupings represented by xe2x80x94(CH2)r, optionally mono- or poly-substituted by fluorine, chlorine or cyano, or chains of the formula xe2x80x94L1xe2x80x94(CH2)rxe2x80x94 or xe2x80x94L1xe2x80x94(CH2)rxe2x80x94L2xe2x80x94(CH2)sxe2x80x94, wherein L1 and L2 represent a single bond or linking functional groups such as xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, R2 represents hydrogen or lower alkyl and r and s are each an integer from 1 to 20, with the proviso that r+s xe2x89xa624;
S5, S6 each independently of the other represents a single covalent bond or divalent groups, such as straight-chain or branched alkylene groupings represented by xe2x80x94(CH2)rxe2x80x94, optionally mono- or poly-substituted by fluorine, chlorine or cyano, or chains of the formula L1xe2x80x94(CH2)rxe2x80x94L2xe2x80x94 or L1xe2x80x94(CH2)rxe2x80x94L2xe2x80x94(CH2)sxe2x80x94L3xe2x80x94, wherein L1, L2 and L3 each independently of the others represents a single bond or linking functional groups such as xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94; wherein R2 represents hydrogen or lower alkyl and r and s are each an integer from 1 to 20, with the proviso that 1xe2x89xa6r+sxe2x89xa624;
E represents an unsubstituted or optionally fluoro-, chloro-, cyano-, alkyl-, alkoxy-, fluoroalkyl- or fluoroalkoxy-substituted aromatic or alicyclic divalent, trivalent or tetravalent group, the valencies of which are distributed between different atoms of the group, or is the nitrogen atom or xe2x80x94CHxe2x80x94;
F represents the radical of an aliphatic, alicyclic or aromatic diamine after formal removal of the two amino groups; and
G represents hydrogen or a monovalent organic group, derived from an alcohol after formal removal of the hydroxy group.
The tetracarboxylic acid dianhydride on which the tetravalent organic radical T1 is based may be aliphatic, alicyclic or aromatic.
Preferred examples of aliphatic or alicyclic tetracarboxylic acid anhydrides are: butanetetracarboxylic acid dianhydride; ethylenemaleic acid dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride; 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride; 2,3,5-tricarboxycyclopentylacetic acid dianhydride; 3,5,6-tricarboxynorbomylacetic acid dianhydride; 2,3,4,5-tetrahydrofiurantetracarboxylic acid dianhydride; 4-(2,5-dioxotetrahydrofuaran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride; 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride; bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride; bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid dianhydride; 1,8-dimethylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.
Examples of preferred aromatic tetracarboxylic acid dianhydrides are: pyromellitic acid dianhydride;
3,3xe2x80x2,4,4xe2x80x2-benzophenonetetracarboxylic acid dianhydride;
4,4xe2x80x2-oxydiphthalic acid dianhydride;
3,3xe2x80x2,4,4xe2x80x2-diphenylsulphonetetracarboxylic acid dianhydride;
1,4,5,8-naphthalenetetracarboxylic acid dianhydride;
2,3,6,7-naphthalenetetracarboxylic acid dianhydride;
3,3xe2x80x2,4,4xe2x80x2-dimethyldiphenylsilanetetracarboxylic acid dianhydride;
3,3xe2x80x2,4,4xe2x80x2-tetraphenylsilanetetracarboxylic acid dianhydride;
1,2,3,4-furantetracarboxylic acid dianhydride;
4,4xe2x80x2-bis(3,4-dicarboxyphenoxy)diphenyl sulphide dianhydride;
4,4xe2x80x2-bis(3,4-dicarboxyphenoxy)diphenyl sulphone dianhydride;
4,4xe2x80x2-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride;
3,3xe2x80x2,4,4xe2x80x2-biphenyltetracarboxylic acid dianhydride; ethylene glycol bis(trimellitic acid) dianhydride;
4,4xe2x80x2-(1,4-phenylene)bisphthalic acid) dianhydride;
4,4xe2x80x2-(1,3-phenylene)bis(phthalic acid) dianhydride;
4,4xe2x80x2-(hexafluoroisopropylidene)diphthalic acid dianhydride;
4,4xe2x80x2-oxydi(1,4-phenylene)bis(phthalic acid) dianhydride; and
4,4xe2x80x2-methylenedi(1,4-phenylene)bis(phthalic acid) dianhydride.
Especially preferred are:
1,2,3,4-cyclobutanetetracarboxylic acid dianhydride;
1,2,3,4-cyclopentanetetracarboxylic acid dianhydride;
2,3,5-tricarboxycyclopentylacetic acid dianhydride;
5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride;
4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride;
4,4xe2x80x2-(hexafluoroisopropylidene)diphthalic acid dianhydride; and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.
The groups T2 and T3 can be derived from aliphatic, alicyclic or aromatic dicarboxylic acid anhydrides.
Preferred groups T2 and T3 are trivalent aromatic or carbocyclic groups, the three valencies of which are so distributed between three different carbon atoms that two of those valencies are located at adjacent carbon atoms.
Especially preferred groups T2 and T3 are trivalent benzene derivatives, the three valencies of which are so distributed between three different carbon atoms that two of those valencies are in the ortho-position relative to one another.
Preferred xe2x80x9cspacer unitsxe2x80x9d S3 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94COxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa620, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S3 are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 3-propyleneoxy, 3-propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentyleneoxy, 5-pentyleneoxycarbonyl, 4-butylenecarbonyloxy, 6-hexyleneoxy, 6-hexyleneoxycarbonyl, 5-pentylenecarbonyloxy, 7-heptyleneoxy, 7-heptyleneoxycarbonyl, 6-hexylenecarbonyloxy, 8-octyleneoxy, 8-octyleneoxycarbonyl, 7-heptylenecarbonyloxy, 9-nonyleneoxy, 9-nonyleneoxycarbonyl, 8-octylenecarbonyloxy, 10-decyleneoxy, 10-decyleneoxycarbonyl, 9-nonylenecarbonyloxy, 11-undecyleneoxy, 11-undecyleneoxycarbonyl, 10-decylenecarbonyloxy, 12-dodecyleneoxy, 12-dodecyleneoxycarbonyl, 11-undecylenecarbonyloxy, 3-propyleneiminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleneiminocarbonyl, 6-hexyleneiminocarbonyl, 7-heptyleneiminocarbonyl, 8-octyleneiminocarbonyl, 9-nonyleneiminocarbonyl, 10-decyleneiminocarbonyl, 11-undecyleneiminocarbonyl, 12-dodecyleneiminocarbonyl, 2-ethylenecarbonylimino, 3-propylenecarbonylimino, 4-butylenecarbonylimino, 5-pentylenecarbonylimino, 6-hexylenecarbonylimino, 7-heptylenecarbonylimino, 8-octylenecarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneoxy)hexylene, 6-(3-propyleneoxy)hexyleneoxy, 6-(3-propyleneiminocarbonyloxy)hexyleneoxy, 6-(3-propyleneiminocarbonyl)hexylene, 6-(3-propyleneiminocarbonyl)hexyleneoxy and the like.
Preferred xe2x80x9cspacer unitsxe2x80x9d S4 and S7 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa620, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S4 and S7 are 1,2-ethylene, 1,3-propylene, 4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 2-oxyethylene, 3-oxypropylene, 4-oxybutylene, 5-oxypentylene, 6-oxyhexylene, 7-oxyheptylene, 8-oxyoctylene, 9-oxynonylene, 10-oxydecylene, 11-oxyundecylene, 12-oxydodecylene, 2-(oxycarbonyl)ethylene, 3-(oxycarbonyl)propylene, 4-(oxycarbonyl)butylene, 5-(oxycarbonyl)pentylene, 6-(oxycarbonyl)hexylene, 7-(oxycarbonyl)heptylene, 8-(oxycarbonyl)octylene, 9-(oxycarbonyl)nonylene, 10-(oxycarbonyl)decylene, 11-(oxycarbonyl)undecylene, 12-(oxycarbonyl)dodecylene, 2-(carbonyloxy)ethylene, 3-(carbonyloxy)propylene, 4-(carbonyloxy)butylene, 5-(carbonyloxy)pentylene, 6-(carbonyloxy)hexylene, 7-(carbonyloxy)heptylene, 8-(carbonyloxy)octylene, 9-(carbonyloxy)nonylene, 10-(carbonyloxy)decylene, 11-(carbonyloxy)undecylene, 12-(carbonyloxy)dodecylene, 2-(carbonylimino)ethylene, 3-(carbonylimino)propylene, 4-(carbonylimino)butylene, 5-(carbonylimino)pentylene, 6-(carbonylimino)hexylene, 7-(carbonylimino)heptylene, 8-(carbonylimino)octylene, 9-(carbonylimino)nonylene, 10-(carbonylimino)decylene, 11-(carbonylimino)undecylene, 12-(carbonylimino)dodecylene, 2-iminoethylene, 3-iminopropylene, 4-iminobutylene, 5-iminopentylene, 6-iminohexylene, 7-iminoheptylene, 8-iminooctylene, 9-iminononylene, 10-iminodecylene, 11-iminoundecylene, 12-iminododecylene, 2-iminocarbonylethylene, 3-iminocarbonylpropylene, 4-iminocarbonylbutylene, 5-iminocarbonylpentylene, 6-iminocarbonylhexylene, 7-iminocarbonylheptylene, 8-iminocarbonyloctylene, 9-iminocarbonylnonylene, 10-iminocarbonyldecylene, 11-iminocarbonylundecylene, 12-iminocarbonyldodecylene, 2-(2-ethyleneoxy)ethylene, 2-(3-propyleneoxy)ethylene, 6-(4-butyleneoxy)hexylene, 2-(2-ethyleneiminocarbonyl)ethylene, 2-(3-propyleneiminocarbonyl)ethylene, 6-(4-butyleneiminocarbonyl)hexylene, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneiminocarbonyl)hexylene and the like.
Preferred xe2x80x9cspacer unitsxe2x80x9d S5 and S6 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2) rxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94COxe2x80x94O(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa620, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S5 and S6 are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 3-propyleneoxy, 3-propylenreoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentyleneoxy, 5-pentyleneoxycarbonyl, 4-butylenecarbonyloxy, 6-hexyleneoxy, 6-hexyleneoxycarbonyl, 5-pentylenecarbonyloxy, 7-heptyleneoxy, 7-heptyleneoxycarbonyl, 6-hexylenecarbonyloxy, 8-octyleneoxy, 8-octyleneoxycarbonyl, 7-heptylenecarbonyloxy, 9-nonyleneoxy, 9-nonyleneoxycarbonyl, 8-octylenecarbonyloxy, 10-decyleneoxy, 10-decyleneoxycarbonyl, 9-nonylenecarbonyloxy, 11-undecyleneoxy, 11-undecyleneoxycarbonyl, 10-decylenecarbonyloxy, 12-dodecyleneoxy, 12-dodecyleneoxycarbonyl, 12-undecylenecarbonyloxy, 3-propyleneiminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleneiminocarbonyl, 6-hexyleneiminocarbonyl, 7-heptyleneiminocarbonyl, 8-octyleneiminocarbonyl, 9-nonyleneiminocarbonyl, 10-decyleneiminocarbonyl, 11-undecyleneiminocarbonyl, 12-dodecyleneiminocarbonyl, 2-ethylenecarbonylimino, 3-propylenecarbonylimino, 4-butylenecarbonylimino, 5-pentylenecarbonylimino, 6-hexylenecarbonylimino, 7-heptylenecarbonylimino, 8-octylenecarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneoxy)hexylene, 6-(3-propyleneoxy)hexyleneoxy, 6-(3-propyleneiminocarbonyloxy)hexyleneoxy, 6-(3-propyleneiminocarbonyl)hexyl, 6-(3-propyleneiminocarbonyl)hexyloxy, 1,2-ethylenedioxy, 1,3-propylenedioxy, 1,4-butylenedioxy, 1,5-pentylenedioxy, 1,6-hexylenedioxy, 1,7-heptylenedioxy, 1,8-octylenedioxy, 1,9-nonylenedioxy, 1,10-decylenedioxy, 1,11-undecylenedioxy, 1,12-dodecylenedioxy and the like.
The radicals F are divalent groups that can be derived from aliphatic, alicyclic or aromatic diamines by formal removal of the amino groups.
Preferred examples of such aliphatic and alicyclic diamines are:
ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, 1,7-heptylenediamine, 1,8-octylenediamine, 1,9-nonylenediamine, 1,10-decylenediamine, 1,11-undecylenediaminei 1,12-dodecylenediamine, xcex1,xcex1xe2x80x2-diamino-m-xylene, xcex1,xcex1xe2x80x2-diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl)methylamine, 1,2-diaminocyclohexane, 4,4xe2x80x2-diaminodicyclohexylmethane, 1,3-bis(methylamino)cyclohexane, 4,9-dioxadodecane-1,12-diamine.
Preferred examples of aromatic diamines are:
3,5-diaminobenzoic acid methyl ester; 3,5-diaminobenzoic acid hexyl ester; 3,5-diaminobenzoic acid dodecyl ester; 3,5-diaminobenzoic acid isopropyl ester; 4,4xe2x80x2-methylenedianiline; 4,4xe2x80x2-ethylenedianiline; 4,4xe2x80x2-diamino-3,3xe2x80x2-dimethyldiphenylmethane; 3,3xe2x80x2,5,5xe2x80x2-tetramethylbenzidine; 4,4xe2x80x2-diaminodiphenyl sulphone; 4,4xe2x80x2-diaminodiphenyl ether; 1,5-diamninonaphthalene; 3,3xe2x80x2-dimethyl-4,4xe2x80x2-diaminobiphenyl; 3,4xe2x80x2-diaminodiphenyl ether; 3,3xe2x80x2-diaminobenzophenone; 4,4xe2x80x2-diaminobenzophenone; 4,4xe2x80x2-diamino-2,2xe2x80x2-dimethylbibenzyl; 2,2-bis[4-(4-aminophenoxy)phenyl]sulphone; 1,4-bis(4-arninophenoxy)benzene; 1,3-bis(4-aminophenoxy)benzene; 1,3-bis(3-aminophenoxy)benzene; 2,7-diarninofluorene; 9,9-bis(4-aminophenyl)fluorene; 4,4xe2x80x2-methylenebis(2-chloroaniline); 4,4-bis(4-aminophenoxy)biphenyl; 2,2xe2x80x2,5,5xe2x80x2-tetrachloro-4,4xe2x80x2-diaminobiphenyl; 2,2xe2x80x2-dichloro-4,4xe2x80x2-diamino-5,5xe2x80x2-dimethoxybiphenyl; 3,3xe2x80x2-dimethoxy-4,4xe2x80x2-diaminobiphenyl; 4,4xe2x80x2-(1,4-phenyleneisopropylidene)bisaniline; 4,4xe2x80x2-(1,3-phenyleneisopropylidene)bisaniline; 2,2-bis[4-(4-aminophenoxy)phenyl]propane; 2,2-bis[3-(4-aminophenoxy)phenyl]hexafluoropropane; 2,2-bis[3-amino-4-methylphenyl]hexafluoropropane; 2,2-bis(4-aminophenyl)hexafluoropropane; 2,2xe2x80x2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane; 4,4xe2x80x2-diamino-2,2xe2x80x2-bis(trifluoromethyl)biphenyl; 4,4xe2x80x2-bis[(4-amino-2-trifluoromethyl)phenoxy]-2,3,5,6,2xe2x80x2,3xe2x80x2,5xe2x80x2,6xe2x80x2-octafluorobiphenyl.
The divalent, trivalent or tetravalent group E serves essentially as a member linking the polymer main chain to the side-chain of the formula I, two of the valencies serving as the linkages, indicated in formulae III to VIII, to S3 to S7 within the main chain. The third and optionally the fourth valency serves as the linkage to one or two side-chain(s) of the formula I. The polymer chain may, however, also comprise building blocks of the formulae III to VIII in which the side-chain of formula I is absent, that is to say where the group E is merely divalent. The proportion of building blocks of the formulae III to VIII in which E is divalent, that is to say in which there is no crosslinkable side-chain of the formula I present, is generally less than 75%, but preferably less than 50% and more especially less than 30%. Of the trivalent and tetravalent groups E that contain one or two crosslinkable side-chains of the formula I, the trivalent groups, that is to say those groups which are linked to only one crosslinkable side-chain of the formula I, are preferred.
The building blocks of the formulae IV, VI and VIII are amidecarboxylic acid groupings or amidecarboxylic acid ester groupings which on the one hand may occur as a result of incomplete imidisation in the polyimide chain. On the other hand, polymers that consist only of building blocks of formulae IV, VI or VIII, that is to say polyamidecarboxylic acids or polyamidecarboxylic acid esters, are important precursors for the preparation of the polyimides according to the invention and are also included in the present invention. Of those polymers which contain groups of formulae IV, VI or VIII, preference is given to those in which G is hydrogen, that is to say those which consist exclusively of, or contain some, polyamidecarboxylic acid groups.
The side-chain polymers according to the invention can be present in the form of homopolymers as well as in the form of copolymers. The term xe2x80x9ccopolymersxe2x80x9d is to be understood as meaning especially statistical copolymers.
The number of monomer building blocks from which the polymer chains according to the invention are synthesised can vary within a wide range. It is generally from 2 to 2000, but especially from 3 to 200.
The preparation of the polyamide acids and polyimides according to the invention is generally carried out analogously to the methods frequently described in the polyimide literature, for example Plast. Eng. 36, (1996).
For example, the polycondensation reaction for the preparation of the polyamide acids is carried out in solution in a polar aprotic organic solvent, such as xcex3-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone or N,N-dimethylformamide. In most cases equimolar amounts of the dianhydride and the diamine are used, that is to say one amino group per anhydride group. If it is desired to stabilise the molecular weight of the polymer, it is possible for that purpose to add an excess or a less than stoichiometric amount of one of the two components or to add a monofunctional compound in the form of a dicarboxylic acid monoanhydride or in the form of a monoamine. Examples of such monofunctional compounds are maleic acid anhydride, phthalic acid anhydride, aniline and so on. The reaction is carried out preferably at a temperature of less than 100xc2x0 C.
The cyclisation of the polyamide acids to form the polyimides can be carried out by heating, that is to say by condensation with removal of water or by other imidisation reactions with reagents. When carried out purely thermally, the imidisation of the polyamide acids is not always complete, that is to say the resulting polyimides may still contain proportions of polyamide acid. The imidisation reactions are generally carried out at a temperature of from 60 to 250xc2x0 C., but preferably at less than 200xc2x0 C. In order to achieve imidisation at rather lower temperatures there are additionally mixed into the reaction mixture reagents that facilitate the removal of water. Such reagents are, for example, mixtures consisting of acid anhydrides, such as acetic acid anhydride, propionic acid anhydride, phthalic acid anhydride, trifluoroacetic acid anhydride, and tertiary amines, such as triethylamine, trimethylamine, tributylamine, pyridine, N,N-dimethylaniline, lutidine, collidine etc. The amount of reagents used in that case is preferably at least two equivalents of amine and four equivalents of acid anhydride per equivalent of polyamide acid to be condensed.
The imidisation reaction can be carried out before or alternatively only after application to a support. The latter variant is preferred especially when the polyimide in question has poor solubility in the customary solvents.
The polymers according to the invention can then be applied to a support and, after any imidisation step which may be necessary, crosslinked by irradiation with linearly polarised light, that is to say by cycloaddition of their side-chains containing the photoreactive 3-arylacryloyl group, there being obtained, depending upon the direction of polarisation of the light radiated in, a preferred direction of orientation and of the angle of tilt for liquid crystals that are bought into contact with the orientation layer. By spatially selective irradiation of the molecular units according to the invention it is hence possible for very specific regions of a surface to be aligned and provided with a defined angle of tilt. At the same time the orientation layer so produced is also stabilised by the cycloaddition.
The present invention therefore relates also to the use of the polymers according to the invention as orientation layers for liquid crystals, and to their use in optical constructional elements, especially in the production of hybrid layer elements.
Such orientation layers can be produced, for example, by first preparing a solution of the resulting polymer material, which is applied to a support, which is optionally coated with an electrode (for example a glass plate coated with indium-tin oxide (ITO)), in a spin-coating apparatus, so that homogeneous layers of 0.05 to 50 xcexcm thickness are produced. Then, or optionally after prior imidisation, the regions to be oriented can be irradiated, for example, with a high-pressure mercury vapour lamp, a xenon lamp or a pulsed UV laser, using a polariser and optionally a mask for creating images of structures. The irradiation time is dependent upon the output of the individual lamps and can vary from a few seconds to several hours. The dimerisation can also be carried out, however, by irradiation of the homogeneous layer using filters that for example, allow only the radiation suitable for the crosslinking reaction to pass through.